The first members of the octasubstituted naphthalene spider-host series with type I (abababab) conformation: gateway to new nano-host gas storage materials.

Octakis(m-tolyloxymethyl)naphthalene, the first Type I spider host produced, crystallises from tetraglyme forming a novel channel structure with the host molecule attaining exact D(2) symmetry. The (flexible) channel structure is retained for guest CS(2), the host now only having exact C(2) symmetry. The octa-sulfone octakis(m-tolylsulfonylmethyl)naphthalene is also of Type I in its triclinic DMSO clathrate. DNMR establishes a substantial difference in molecular flexibilities in solution.